US4657693A - Spray-dried granular detergent compositions containing tripolyphosphate detergent builder, polyethylene glycol and polyacrylate - Google Patents
Spray-dried granular detergent compositions containing tripolyphosphate detergent builder, polyethylene glycol and polyacrylate Download PDFInfo
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- US4657693A US4657693A US06/814,021 US81402185A US4657693A US 4657693 A US4657693 A US 4657693A US 81402185 A US81402185 A US 81402185A US 4657693 A US4657693 A US 4657693A
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- United States
- Prior art keywords
- polyacrylate
- polyethylene glycol
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- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 37
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 34
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 33
- 239000003599 detergent Substances 0.000 title claims abstract description 19
- 235000019832 sodium triphosphate Nutrition 0.000 title claims description 9
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 alkali metal tripolyphosphate Chemical class 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 7
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 3
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 239000000463 material Substances 0.000 description 21
- 229910000323 aluminium silicate Inorganic materials 0.000 description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 238000005342 ion exchange Methods 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 229930182556 Polyacetal Natural products 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000003147 glycosyl group Chemical group 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- VJSWLXWONORKLD-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-trisulfonic acid Chemical compound OC1=C(S(O)(=O)=O)C(O)=C(S(O)(=O)=O)C(O)=C1S(O)(=O)=O VJSWLXWONORKLD-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002004 Pluronic® R Polymers 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JIBFYZIQZVPIBC-UHFFFAOYSA-L dipotassium;2-(carboxymethoxy)propanedioate Chemical compound [K+].[K+].OC(=O)COC(C([O-])=O)C([O-])=O JIBFYZIQZVPIBC-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012188 paraffin wax Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229960000502 poloxamer Drugs 0.000 description 1
- 229920001987 poloxamine Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M toluenesulfonate group Chemical class C=1(C(=CC=CC1)S(=O)(=O)[O-])C LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-M xylenesulfonate group Chemical group C1(C(C=CC=C1)C)(C)S(=O)(=O)[O-] GDJZZWYLFXAGFH-UHFFFAOYSA-M 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
Definitions
- the present invention relates to spray-dried, granular detergent compositions.
- the present invention encompasses a spray dried granular detergent composition comprising:
- the detergent compositions of the present invention contain a nonsoap anionic detergent surfactant, a water-soluble alkali metal tripolyphosphate detergent builder, and a mixture of a polyacrylate polymer of selected molecular weight and a polyethylene glycol of selected molecular weight.
- the polyacrylate/polyethylene glycol mixtures herein provides a surprising boost to dispersion rates in cold water and improvement in physical properties.
- compositions of the present invention are prepared by spray drying and have superior physical characteristics.
- the detergent compositions herein contain from about 5% to about 50%, preferably from about 10% to about 30% of a nonsoap anionic surfactant, or mixtures thereof.
- Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,929,678, Laughlin et al, issued Dec. 30, 1975, both incorporated herein by reference.
- Useful anionic surfactants include the water-soluble salts, preferably the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383 both of which are incorporated herein by reference.
- Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11-13 LAS.
- anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
- Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acryl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin or paraffin sulfonates containing from about 12 to 18 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to about 3 carbon atoms in the alkyloxy group and from about 8 to about 20 carbon atoms in the alkane moiety.
- Particularly preferred surfactants for use herein include sodium C 11-13 LAS, C 14-18 alkyl sulfates, C 14-18 alkyl linear polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide, and mixtures thereof.
- compositions of the present invention contain from about 20% to about 60%, preferably from about 30% to about 50%, by weight of an alkali metal tripolyphosphate, preferably sodium tripolyphosphate.
- compositions of the present invention contain from about 1% to about 10%, preferably from about 1.5% to about 8% of a mixture of a polyethylene glycol and a polyacrylate.
- the polyethylene glycol and the polyacrylate are present in a weight ratio of from about 1:10 to about 10:1, preferably from about 1:3 to about 3:1.
- the polyethylene glycol has a weight average molecular weight of from about 1,000 to about 50,000, preferably from about 4,000 to about 20,000.
- the polyacrylate has a weight average molecular weight of from about 1,000 to about 20,000, preferably from about 2,000 to about 10,000, more preferably from about 3,000 to about 8,000.
- polyethylene glycols are preferred, other suitable polymeric materials are the condensation products of C 10-20 alcohols or C 8-18 alkyl phenols with sufficient ethylene oxide, i.e., more than 50% by weight of the polymer, so that the resultant product has a melting point above about 35° C.
- Preferred polymers contain at least about 70% ethylene oxide by weight and more preferred polymers contain at least about 80% ethylene oxide by weight.
- Preferred polymeric materials have HLB values of at least about 15, and more preferably at least about 17.
- Block and heteric polymers based on ethylene oxide and propylene oxide addition to a low molecular weight organic compound containing one or more active hydrogen atoms are suitable in the practice of the invention.
- Polymers based on the addition of ethylene oxide and propylene oxide to propylene glycol, ethylenediamine, and trimethylolpropane are commercially available under the names Pluronics®, Pluronic® R, Tetronics® and Pluradots® from the BASF Wyandotte Corporation of Wyandotte, Mich.
- Corresponding nonproprietary names of the first three trade names are poloxamer, meroxapol and poloxamine, respectively.
- Optimum solubility of the polyacrylate is obtained when it is in the form of an at least partially neutralized alkali metal salts.
- the sodium salts are most preferred.
- Suitable polyacrylates herein are the partially or fully neutralized salts of polymers of acrylic acid.
- the percentage by weight of the polyacrylate units which is derived from acrylic acid is preferably greater than about 80%.
- Suitable copolymerizable monomers include, for example, methacrylic acid, hydroxyacrylic acid, vinyl chloride, vinyl alcohol, furan, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrene, alpha-methylstyrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and 3-butenoic acid. Mixtures of these polymers can also be used.
- the polyacrylate may also be added in the acid form and neutralized by various bases present.
- Preferred copolymers of the above group contain at least about 90% by weight of units derived from the acrylic acid. Preferably essentially all of the polymer is derived from acrylic acid. Particularly preferred is sodium polyacrylate, especially when it is has an average molecular weight of from about 3,000 to about 8,000.
- compositions of the invention can additionally contain up to 10%, preferably about 5% of an organic surfactant selected from the group consisting of non-ionic, zwitterionic, ampholytic, and cationic surfactants and mixtures thereof.
- organic surfactant selected from the group consisting of non-ionic, zwitterionic, ampholytic, and cationic surfactants and mixtures thereof.
- the compositions can also contain other conventional ingredients, such as nonphosphorous builders, either organic or inorganic in nature.
- Useful nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to about 12 moles of ethylene oxide per mole of alkyl phenol.
- Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from about 8 to about 22 carbon atoms, in either straight chain or branched configuration, with from about 3 to about 12 moles of ethylene oxide per mole of alcohol.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to about 15 carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of alcohol.
- Suitable semi-polar nonionic surfactants include: (2) water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms, (2) water-soluble phosphine oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 2 to 3 carbon atoms and (3) water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
- Optional ampholytic surfactants include derivatives of aliphatic, or aliphatic derivatives of heterocyclic, secondary and tertiary amines in which the aliphatic moiety can be straight chain, or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Useful cationic surfactants include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy, issued Dec. 16, 1980, both incorporated herein by reference.
- Optional zwitterionic surfactants include derivatives of aliphatic quaternary ammonium or phosphonium or ternary sulfonium compounds in which one of the aliphatic substituents contains from about 8 to about 18 carbon atoms.
- alkylpolysaccharide surfactants are also useful in the compositions of the invention.
- the preferred alkylpolyglycosides have the formula RO(C n H 2n O) t (glycosyl) x wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms, n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0, and x is about 1-1/2 to about 10, preferably from about 1-1/2 to about 3, preferably from about 1.6 to about 2.7.
- the glycosyl is preferably derived from glucose.
- the detergent compositions of the invention can optionally contain water-insoluble aluminosilicate ion exchange material of the formula
- Amorphous hydrated aluminosilicate materials useful herein have the empirical formula
- M is sodium, potassium, ammonium or substituted ammonium
- z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate.
- the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
- the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
- Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
- particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
- the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaCO 3 water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg. eq./g. to about 352 mg. eq./g.
- the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
- Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
- the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange capacity of at least about 50 mg. eq. CaCO 2 /g. (12 mg. Mg ++ /g.) and a Mg ++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
- Aluminosilicate ion exchange material useful in the practice of this invention are commercially available.
- the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
- a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel, et al, issued Oct. 12, 1976, incorporated herein by reference.
- Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
- the crystalline aluminosilicate ion exchange material has the formula
- x is from about 20 to about 30, especially about 27.
- Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium, carboxylates, nonpolymeric polycarboxylates and polyhydroxysulfonates.
- nonpolymeric polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
- the compositions of this invention only contain the limited amount of polyacrylate defined hereinafter.
- polyacetal carboxylates are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 to Crutchfield, et al, and U.S. Pat. No. 4,146,495, issued Mar. 27, 1979 to Crutchfield, et al, both incorporated herein by reference.
- These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, and converted to the corresponding.
- compositions herein preferably contain from about 0% to about 10%, preferably from about 0.5% to about 8%, and most preferably from about 1% to about 6%, by weight of an alkali metal silicate having a molar ratio of SiO 2 to alkali metal oxide of from about 1.0 to about 3.2, preferably from about 1.4 to about 2.4.
- Sodium silicate, particularly one having a molar ratio of about 1.6 to about 2.2 is preferred.
- the alkali metal silicates can be purchased in either liquid or granular form. Silicate slurries can conveniently be used to avoid having to dissolve the dried form in the crutcher mix of the components herein.
- compositions of the present invention can be included in the compositions of the present invention.
- these include color speckles, bleaching agents such as perborates and percarbonates and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, coil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes such a toluene sulfonates and xylene sulfonates, enzymes, enzyme-stabilizing agents, perfumes and water.
- compositions of the present invention can comprise a portion of compositions containing a wide variety of materials suitable for detergent or other uses.
- a base product was prepared by spray drying according to the following formula.
- the base product was produced according to Example I with varying ratios of polyethylene glycol (PEG) with a weight average molecular weight of 8,000 and sodium polyacrylate with weight average molecular weight of 4,500 as shown below added in the crutcher mix.
- PEG polyethylene glycol
- Eight-five grams (85 g.) of product was sewn into black fabric pockets and agitated on delicate agitation at 60° F. (15.5° C.) in a Kenmore washer. Pockets were removed and cut at 5 minutes and 10 minutes and graded on a 1-7 scale where 1 is poorly dispersed with most of the product remaining caked in the pocket and 7 is completely dispersed. Grades reported are averages of two replicate tests.
- the products containing both the PEG and polyacrylate of the invention have the most improved cold water dispersion.
- a crutcher paste was prepared with the following composition.
- Samples were prepared with the following additive parts to 17.5 parts anionic surfactant. Added water was kept constant at 1.5 parts.
- the sample with the mixture of PEG/polyacrylate was overall less viscous at elevated processing-range temperatures than the control or samples with only PEG or polyacrylate, while remaining crystalline at room temperature.
- This crystalline property usually translates into crisp, non-sticky free-flowing granules with good physical properties, i.e., storage stability, pourability, and caking resistance.
- the PEG/polyacrylate sample was consistantly a thin fluid at high temperatures, while showing the best stability at room temperature. This increases ease of processing along with increased storage stability of the finished granule.
- the sample with the PEG/polyacrylate mixture showed desirable phase continuity.
- a dominent or external lye phase is desirable as it translates into non-sticky free flowing finished granules and more rapid dissolution or dispersion in wash water.
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Abstract
Detergent compositions comprising a mixture of polyethylene glycol and polyacrylate of specified molecular weight for improved physical properties and cold water dispersion are disclosed.
Description
This is a continuation of Ser. No. 664,905, filed on Oct. 26, 1984, now abandoned.
The present invention relates to spray-dried, granular detergent compositions.
The present invention encompasses a spray dried granular detergent composition comprising:
(a) from about 5% to about 50% by weight of a nonsoap anionic detergent surfactant;
(b) from about 20% to about 60% by weight of an alkali metal tripolyphosphate detergent builder;
(c) from about 1% to about 10% of a mixture of a polyethylene glycol and a polyacrylate, said mixture having a polyethylene glycol:polyacrylate weight ratio of from about 1:10 to about 10:1, said polyethylene glycol having a weight average molecular weight of from about 1,000 to about 50,000, and said polyacrylate having a weight average molecular weight of from about 1,000 to about 20,000.
The detergent compositions of the present invention contain a nonsoap anionic detergent surfactant, a water-soluble alkali metal tripolyphosphate detergent builder, and a mixture of a polyacrylate polymer of selected molecular weight and a polyethylene glycol of selected molecular weight. The polyacrylate/polyethylene glycol mixtures herein provides a surprising boost to dispersion rates in cold water and improvement in physical properties.
The compositions of the present invention are prepared by spray drying and have superior physical characteristics.
The detergent compositions herein contain from about 5% to about 50%, preferably from about 10% to about 30% of a nonsoap anionic surfactant, or mixtures thereof. Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,929,678, Laughlin et al, issued Dec. 30, 1975, both incorporated herein by reference.
Useful anionic surfactants include the water-soluble salts, preferably the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8 -C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383 both of which are incorporated herein by reference. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-13 LAS.
Other anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acryl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin or paraffin sulfonates containing from about 12 to 18 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to about 3 carbon atoms in the alkyloxy group and from about 8 to about 20 carbon atoms in the alkane moiety.
Particularly preferred surfactants for use herein include sodium C11-13 LAS, C14-18 alkyl sulfates, C14-18 alkyl linear polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide, and mixtures thereof.
The compositions of the present invention contain from about 20% to about 60%, preferably from about 30% to about 50%, by weight of an alkali metal tripolyphosphate, preferably sodium tripolyphosphate.
The compositions of the present invention contain from about 1% to about 10%, preferably from about 1.5% to about 8% of a mixture of a polyethylene glycol and a polyacrylate. The polyethylene glycol and the polyacrylate are present in a weight ratio of from about 1:10 to about 10:1, preferably from about 1:3 to about 3:1. The polyethylene glycol has a weight average molecular weight of from about 1,000 to about 50,000, preferably from about 4,000 to about 20,000. The polyacrylate has a weight average molecular weight of from about 1,000 to about 20,000, preferably from about 2,000 to about 10,000, more preferably from about 3,000 to about 8,000.
While polyethylene glycols are preferred, other suitable polymeric materials are the condensation products of C10-20 alcohols or C8-18 alkyl phenols with sufficient ethylene oxide, i.e., more than 50% by weight of the polymer, so that the resultant product has a melting point above about 35° C.
Preferred polymers contain at least about 70% ethylene oxide by weight and more preferred polymers contain at least about 80% ethylene oxide by weight. Preferred polymeric materials have HLB values of at least about 15, and more preferably at least about 17. Block and heteric polymers based on ethylene oxide and propylene oxide addition to a low molecular weight organic compound containing one or more active hydrogen atoms are suitable in the practice of the invention. Polymers based on the addition of ethylene oxide and propylene oxide to propylene glycol, ethylenediamine, and trimethylolpropane are commercially available under the names Pluronics®, Pluronic® R, Tetronics® and Pluradots® from the BASF Wyandotte Corporation of Wyandotte, Mich. Corresponding nonproprietary names of the first three trade names are poloxamer, meroxapol and poloxamine, respectively.
Optimum solubility of the polyacrylate is obtained when it is in the form of an at least partially neutralized alkali metal salts. The sodium salts are most preferred.
Suitable polyacrylates herein are the partially or fully neutralized salts of polymers of acrylic acid. One can also use copolymers formed with small amounts of other copolymerizable monomers. The percentage by weight of the polyacrylate units which is derived from acrylic acid is preferably greater than about 80%. Suitable copolymerizable monomers include, for example, methacrylic acid, hydroxyacrylic acid, vinyl chloride, vinyl alcohol, furan, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrene, alpha-methylstyrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and 3-butenoic acid. Mixtures of these polymers can also be used. The polyacrylate may also be added in the acid form and neutralized by various bases present.
Preferred copolymers of the above group contain at least about 90% by weight of units derived from the acrylic acid. Preferably essentially all of the polymer is derived from acrylic acid. Particularly preferred is sodium polyacrylate, especially when it is has an average molecular weight of from about 3,000 to about 8,000.
It is essential that this mixture be added in the crutcher rather than post dosed for the benefits of the invention to be seen.
The compositions of the invention can additionally contain up to 10%, preferably about 5% of an organic surfactant selected from the group consisting of non-ionic, zwitterionic, ampholytic, and cationic surfactants and mixtures thereof. The compositions can also contain other conventional ingredients, such as nonphosphorous builders, either organic or inorganic in nature.
Useful nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 3 to about 12 moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from about 8 to about 22 carbon atoms, in either straight chain or branched configuration, with from about 3 to about 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to about 15 carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of alcohol.
Suitable semi-polar nonionic surfactants include: (2) water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms, (2) water-soluble phosphine oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 2 to 3 carbon atoms and (3) water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Optional ampholytic surfactants include derivatives of aliphatic, or aliphatic derivatives of heterocyclic, secondary and tertiary amines in which the aliphatic moiety can be straight chain, or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Useful cationic surfactants include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. No. 4,239,659, Murphy, issued Dec. 16, 1980, both incorporated herein by reference.
Optional zwitterionic surfactants include derivatives of aliphatic quaternary ammonium or phosphonium or ternary sulfonium compounds in which one of the aliphatic substituents contains from about 8 to about 18 carbon atoms.
Also useful in the compositions of the invention are alkylpolysaccharide surfactants. The preferred alkylpolyglycosides have the formula RO(Cn H2n O)t (glycosyl)x wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which said alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms, n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0, and x is about 1-1/2 to about 10, preferably from about 1-1/2 to about 3, preferably from about 1.6 to about 2.7. The glycosyl is preferably derived from glucose.
The detergent compositions of the invention can optionally contain water-insoluble aluminosilicate ion exchange material of the formula
Na.sub.z [(AlO.sub.2).sub.z.(SiO.sub.2).sub.y ].xH.sub.2 O
wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.5 and x is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula
M.sub.z (zAlO.sub.2.ySiO.sub.2)
wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate.
The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaCO3 water hardness/g. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg. eq./g. to about 352 mg. eq./g. The aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness. Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
The amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange capacity of at least about 50 mg. eq. CaCO2 /g. (12 mg. Mg++ /g.) and a Mg++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
Aluminosilicate ion exchange material useful in the practice of this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel, et al, issued Oct. 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula
Na.sub.12 [AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].xH.sub.2 O
wherein x is from about 20 to about 30, especially about 27.
Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium, carboxylates, nonpolymeric polycarboxylates and polyhydroxysulfonates. Examples of nonpolymeric polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. The compositions of this invention only contain the limited amount of polyacrylate defined hereinafter.
Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, and phloroglucinol trisulfonate.
Other suitable nonpolymeric polycarboxylates are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 to Crutchfield, et al, and U.S. Pat. No. 4,146,495, issued Mar. 27, 1979 to Crutchfield, et al, both incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, and converted to the corresponding.
The compositions herein preferably contain from about 0% to about 10%, preferably from about 0.5% to about 8%, and most preferably from about 1% to about 6%, by weight of an alkali metal silicate having a molar ratio of SiO2 to alkali metal oxide of from about 1.0 to about 3.2, preferably from about 1.4 to about 2.4. Sodium silicate, particularly one having a molar ratio of about 1.6 to about 2.2 is preferred.
The alkali metal silicates can be purchased in either liquid or granular form. Silicate slurries can conveniently be used to avoid having to dissolve the dried form in the crutcher mix of the components herein.
Other ingredients commonly used in detergent compositions can be included in the compositions of the present invention. These include color speckles, bleaching agents such as perborates and percarbonates and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, coil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes such a toluene sulfonates and xylene sulfonates, enzymes, enzyme-stabilizing agents, perfumes and water.
The detergent compositions of the present invention can comprise a portion of compositions containing a wide variety of materials suitable for detergent or other uses.
The following nonlimiting examples illustrate the detergent compositions of the present invention.
All percentages, parts, and ratios used herein are by weight unless otherwise specified.
A base product was prepared by spray drying according to the following formula.
NaC11-13 LAS: 8.75
NaC14-15 alkyl sulfate: 8.75
Na tripolyphospate: 38.3
Na Silicate solids (1.6r): 5.5
Na sulfate: 13.9
Na Carbonate (dry mixed): 15.5
Na carboxymethylcellulose: 0.35
Ultramarine blue: 0.16
Minor ingredients and water: balance
The base product was produced according to Example I with varying ratios of polyethylene glycol (PEG) with a weight average molecular weight of 8,000 and sodium polyacrylate with weight average molecular weight of 4,500 as shown below added in the crutcher mix. Eight-five grams (85 g.) of product was sewn into black fabric pockets and agitated on delicate agitation at 60° F. (15.5° C.) in a Kenmore washer. Pockets were removed and cut at 5 minutes and 10 minutes and graded on a 1-7 scale where 1 is poorly dispersed with most of the product remaining caked in the pocket and 7 is completely dispersed. Grades reported are averages of two replicate tests.
______________________________________ % 4500 mw 5 minute 10 minute Product PEG % polyacrylate grade grade ______________________________________ A 0 1.0 4.5 6.0 B 0.5 1.0 6.5 7.0 C 0.6 0.5 2.5 4.0 D 1.1 0 2.0 2.75 E 1.1 0 2.0 3.0 ______________________________________
As can be seen, the products containing both the PEG and polyacrylate of the invention have the most improved cold water dispersion.
A crutcher paste was prepared with the following composition.
______________________________________ Weight Percent ______________________________________ Surfactant 27% 1:1 mixture of NaC.sub.11-13 LAS NaC.sub.14-15 alkyl sulfate Water 58% Sodium sulfate and unreacted Balance ______________________________________
Samples were prepared with the following additive parts to 17.5 parts anionic surfactant. Added water was kept constant at 1.5 parts.
Control--No additives
A--1% PEG 8000
B--1% Polyacrylate
C--1% of a 1:1 mixture of PEG and polyacrylate
The samples were placed in an oven for several hours. Rapid observational comparisons were made of these variants; viscosity, stirred viscosity and phase continuity. A filter paper wicking test was used to indicate whether the lye or surfactant phase was dominant or external (i.e., lye or aqueous phase wicks or wets through immediately while a dominant or continuous surfactant phase slows or prevents wicking).
______________________________________ Top Layer Fluidity 1 - no flow; 3 - stiff, but flows; 5 - fluid, creamy; 7 - watery thin Sample Temp (°F.) Control A B C ______________________________________ 72 5 1 5 1 100 4 6 4 6 120 5 5 4 6 140 1 6 4 6 160 2 7 4 6 185 2 7 4 7 ______________________________________
As can be seen, the sample with the mixture of PEG/polyacrylate was overall less viscous at elevated processing-range temperatures than the control or samples with only PEG or polyacrylate, while remaining crystalline at room temperature. This crystalline property usually translates into crisp, non-sticky free-flowing granules with good physical properties, i.e., storage stability, pourability, and caking resistance.
______________________________________ Fluidity, stirred 1 - thickest; 2 - thick/mayonnaise; 4 - pudding-like; 6 - creamy; 7 - watery/thin Sample Temp (°F.) Control A B C ______________________________________ 72 4 2 7 1 100 5 7 7 7 120 7 7 6 7 140 2 7 6 7 160 2 7 6 7 185 2 7 5 7 ______________________________________
Again, the PEG/polyacrylate sample was consistantly a thin fluid at high temperatures, while showing the best stability at room temperature. This increases ease of processing along with increased storage stability of the finished granule.
______________________________________ Phase continuous Sample Temp (°F.) Control A B C ______________________________________ 72 lye lye lye lye 100 lye lye lye lye 120 marginal lye lye lye 140 organic lye lye lye 160 organic lye lye# lye 185 organic lye lye# lye ______________________________________ #Two phase incompatibility (separation)
The sample with the PEG/polyacrylate mixture showed desirable phase continuity. A dominent or external lye phase is desirable as it translates into non-sticky free flowing finished granules and more rapid dissolution or dispersion in wash water.
When taken together, the results of the paste tests clearly show that the PEG/polyacrylate mixture shows better physical characteristics in the paste form. These would translate into better physical characteristics such as storage stability and caking resistance in the finished granular product.
Claims (16)
1. A spray-dried granular detergent composition comprising:
(a) from about 5% to about 50% of a nonsoap anionic surfactant or mixtures thereof;
(b) from about 20% to about 60% of an alkali metal tripolyphosphate builder or mixtures thereof;
(c) from about 1% to about 10% of a mixture of polyethylene glycol and a polyacrylate,
said mixture having a polyethylene glycol to polyacrylate weight ratio of from about 1:3 to about 3:1, said polyethylene glycol having a weight average molecular weight of from about 1,000 to about 50,000, and said polyacrylate having a weight average molecular weight of from about 1,000 to about 20,000.
2. The composition of claim 1 wherein the mixture of polyethylene glycol and polyacrylate comprises from about 1% to about 3% of the composition.
3. The composition of claim 2 wherein the polyacrylate has a weight average molecular weight of from about 2,000 to about 10,000.
4. The composition of claim 3 wherein the polyethylene glycol has a weight average of from about 4,000 to about 20,000, and the polyacrylate has a weight average molecular weight of from about 3,000 to about 8,000.
5. The composition of claim 4 wherein the polyacrylate is sodium polyacrylate.
6. The composition of claim 1 wherein the mixture of polyethylene glycol and polyacrylate are present in a weight ratio of from about 1:3 to about 3:1.
7. The composition of claim 1 wherein the polyacrylate has a weight average molecular weight of from about 3,000 to about 8,000, and the polyethylene glycol has a weight average molecular weight of from about 4,000 to about 20,000.
8. The composition of claim 1 wherein the polyacrylate is sodium polyacrylate.
9. The composition of claim 1 wherein the alkali metal tripolyphosphate builder is sodium tripolyphosphate.
10. The composition of claim 9 wherein the nonsoap anionic surfactant comprises a surfactant selected from the group consisting of alkali metal salts of C11-13 alkylbenzene sulfonates, C14-18 alkyl sulfates, C14-18 alkyl polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide and mixtures thereof.
11. The composition of claim 10 comprising from about 10% to about 30% of the nonsoap anionic surfactant.
12. The composition of claim 9 additionally comprising from about 1% to about 8% by weight of an alkali metal silicate having a molar ratio of from about 1.6 to about 2.4.
13. The composition of claim 12 comprising from about 1% to about 3% of a mixture of a polyethylene glycol and sodium polyacrylate, said mixture having a polyethylene glycol to sodium polyacrylate weight ratio of from about 1:3 to about 3:1, said polyethylene glycol having a weight average molecular weight of from about 4,000 to about 20,000 and said sodium polyacrylate having a weight average molecular weight of from about 3,000 to about 8,000.
14. A process for spray drying a granular detergent composition comprising:
(a) from about 5% to about 50% of a nonsoap anionic surfactant or mixtures thereof;
(b) from about 20% to about 60% of an alkali metal tripolyphosphate builder or mixtures thereof;
(c) from about 1% to about 10% of a mixture of polyethylene glycol and a polyacrylate wherein the polyethylene glycol and polyacrylate are present in a weight ratio of from about 1:3 to about 3:1 and,
wherein the components are mixed in the crutcher along with enough additional water so that the water content of the crutcher paste is from about 25% to about 50% and then spray dried with an inlet air temperature of from about 400° F. (204° C.) to about 800° F. (427° C.).
15. The process of claim 14 wherein the water content of the crutcher paste is from about 28% to about 40% and the inlet air temperature in the spray tower is from about 500° F. (260° C.) to about 700° F. (371° C.).
16. A granular composition prepared by the process of claim 14.
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US06/814,021 US4657693A (en) | 1984-10-26 | 1985-12-23 | Spray-dried granular detergent compositions containing tripolyphosphate detergent builder, polyethylene glycol and polyacrylate |
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US66490584A | 1984-10-26 | 1984-10-26 | |
US06/814,021 US4657693A (en) | 1984-10-26 | 1985-12-23 | Spray-dried granular detergent compositions containing tripolyphosphate detergent builder, polyethylene glycol and polyacrylate |
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US66490584A Continuation | 1984-10-26 | 1984-10-26 |
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Cited By (11)
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US4842761A (en) * | 1988-03-23 | 1989-06-27 | International Flavors & Fragrances, Inc. | Compositions and methods for controlled release of fragrance-bearing substances |
US4931203A (en) * | 1987-06-05 | 1990-06-05 | Colgate-Palmolive Company | Method for making an automatic dishwashing detergent powder by spraying drying and post-adding nonionic detergent |
US5049303A (en) * | 1988-11-09 | 1991-09-17 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions containing a mixture of an ethylene oxide/propylene oxide block copolymer and a polycarboxylate |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5180515A (en) * | 1989-07-27 | 1993-01-19 | The Procter & Gamble Company | Granular detergent compositions having low levels of potassium salt to provide improved solubility |
WO1995025783A1 (en) * | 1994-03-24 | 1995-09-28 | The Procter & Gamble Company | Enzyme granulates |
US5614485A (en) * | 1990-07-10 | 1997-03-25 | The Procter & Gamble Company | Process for making a granular dishwashing composition by agglomerating ingredients and admixing solid alkali metal silicate |
US5756444A (en) * | 1996-11-01 | 1998-05-26 | The Procter & Gamble Company | Granular laundry detergent compositions which are substantially free of phosphate and aluminosilicate builders |
US5759978A (en) * | 1995-12-06 | 1998-06-02 | Basf Corporation | Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and polyalkylene oxide homopolymers |
US5783547A (en) * | 1994-03-24 | 1998-07-21 | The Procter & Gamble Company | Enzyme granulates |
WO2012021761A1 (en) * | 2010-08-12 | 2012-02-16 | Church & Dwight Co., Inc. | Detergent pouch with improved properties |
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---|---|---|---|---|
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WO1995025783A1 (en) * | 1994-03-24 | 1995-09-28 | The Procter & Gamble Company | Enzyme granulates |
US5783547A (en) * | 1994-03-24 | 1998-07-21 | The Procter & Gamble Company | Enzyme granulates |
US5759978A (en) * | 1995-12-06 | 1998-06-02 | Basf Corporation | Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and polyalkylene oxide homopolymers |
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WO2012021761A1 (en) * | 2010-08-12 | 2012-02-16 | Church & Dwight Co., Inc. | Detergent pouch with improved properties |
US9242774B2 (en) | 2010-08-12 | 2016-01-26 | Church & Dwight Co., Inc. | Detergent pouch with improved properties |
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